Rapid setting non-elastomeric polyurethane compositions containing a non-hydroxyl containing ester-modified polyoxylkylene compound

ABSTRACT

Mixtures comprising a low molecular weight polyol having a functionality of from 3 to about 8, a liquid modifier compound having a boiling point above 150°C, such as an ester-modified polyoxyalkylene compound having an average molecular weight above about 700, a polyisocyanate and a non-amine-containing catalyst, instantly set, after a brief induction period, to a solid, dense, non-elastomeric polymeric product which can be demolded within a period of from less than about 1 minute to about 5 minutes.

CROSS REFERENCE TO RELATED APPLICATION

This application is a division of our copending application Ser. No.425,467, filed Dec. 17, 1973 which is a continuation-in-part of ourcopending application Ser. No. 366,835, filed June 4, 1973, now U.S.Pat. No. 3,878,157 which is a continuation-in-part of application Ser.No. 179,149, filed Sept. 9, 1971, now abandoned.

This invention relates to polyurethane compositions and moreparticularly relates to rapid-setting, solid, dense, non-elastomericpolyurethane compositions.

Rapid setting dense, opaque polyurethane compositions have been taughtin U.S. Pat. No. 3,378,511. Such compositions employ, as one of theessential ingredients, a liquid plasticizer which is a dicarboxylic acidester. These compositions while useful in many applications, have somedisadvantages in that they are not readily paintable and are susceptibleto degradation in such common solvents as acetone, methyl isobutylketone, methylene chloride, ethylene dichloride, ethyl acetate,tetrahydrofuran and the like.

The present invention provides one or more of the following advantagesover the prior art, i.e., improved detail reproduction in ornamentalcastings having intricate detail, improved paintability, improvedsolvent resistance, improved lubricity in cast gears and other machineelements and the like.

It is an object of the present invention to provide a rapid-setting,dense, rigid polyurethane composition.

Another object of the present invention is to provide rapid-setting,non-elastomeric, opaque polyurethane compositions.

A further object of the present invention is to provide rapid-setting,dense, non-elastomeric, transparent polyurethane compositions.

These and other objects will become apparent from a reading of thefollowing detailed specification.

The present invention concerns a composition which comprises a polyetherpolyol, an organic polyisocyanate and a non-amine-containing catalystfor urethane formation, characterized in that it contains a liquidmodifier compound having a boiling point above about 150°C selected fromthe group consisting of hydroxyl-containing and non-hydroxyl-containingpolyoxyalkylene compounds, ester-modified polyoxyalkylene compounds,fatty acids, naturally occurring fatty oils, organic phosphates, organicphosphites, organic phosphonates, cyclic ethers, non-ester-containingaromatic compounds, partially hydrogenated aromatic compounds, organiccarbonates, halogenated aliphatic compounds, cyclic sulfones andmixtures thereof.

All the liquid modifier compounds have at least two points in common.They are (1) an apparent ability to act as a heat sink to preventexcessive bubbling which would result from the heat generated by theexothermic heat of reaction and (2) they have boiling points atatmospheric pressure above about 150°C.

The term non-elastomeric polyurethane as employed herein is defined as apolyurethane product having an elongation value of less than 80 percentand the term dense is defined as a density of at least about 1 gram/cc.

Non-elastomeric, rapid-setting, polyurethane compositions are obtainedby intimately admixing together a composition comprising

A. a polyether polyol which is the adduct of a polyhydric initiatorcompound having a functionality of from 3 to about 8 with a vicinalepoxy compound, said polyol having a hydroxyl equivalent weight of atleast about 75 and less than about 230;

B. an organic polyisocyanate;

C. a liquid modifier compound having a boiling point above about 150°Cat atmospheric pressure including for example hydroxyl-containing andnon-hydroxyl-containing polyoxyalkylene compounds, fatty acids,naturally occurring fatty oils, organic phosphates, organic phosphites,organic phosphonates, cyclic ethers, non-ester containing aromaticcompounds, partially hydrogenated aromatic compounds, organiccarbonates, halogenated aliphatic compounds, cyclic sulfones, andmixtures thereof in any combination, and

D. a non-amine containing catalyst for urethane formation;

and wherein Components (A) and (B) are present in amounts so as toprovide an NCO:OH ratio of from about 0.8:1 to about 2:1 and preferablyfrom about 0.95:1 to about 1.1:1; Component C is present in quantitiesof from about 20-50% and preferably from about 30-50% with the provisothat when component (B) is a prepolymer containing less than about 40%NCO groups by weight, then component (C) is present in quantities offrom about 10% to about 50% by weight of the sum of Components (A), (B),and (C); and (D) is present in quantities of from about 0.2 to about10%, preferably from about 0.2 to about 3%, and most preferably fromabout 0.5 to about 3% by weight of the sum of the weights of Components(A), (B) and (C); with the proviso that when Component (C) is ahalogenated aliphatic compound, it is employed in a range of from about0.2 to about 50 percent by weight of the sum of the weights ofComponents (A), (B) and (C); that when the halogenated aliphaticcompound also contains hydroxyl groups and has an OH equivalent weightof less than about 500, it is employed in quantities of from about 0.2to about 5 percent by weight based upon the sum of the weight ofComponents (A), (B) and (C), and that when Component (C) is anon-ester-containing aromatic compound or a halogenated aliphaticcompound, the non-amine-containing catalyst, Component (D), is employedin quantities of from about 0.01 to about 10 percent by weight of thecombined weights of Components (A), (B) and (C).

Suitable initiator compounds having from 3 to 8 hydroxyl groups whichcan be employed to prepare the polyols (Component A) employed in thepresent invention include, for example, glycerine, trimethylolpropane,pentaerythritol, sorbitol, sucrose, mixtures thereof and the like.

Suitable vicinal epoxy compounds which may be reacted with the initiatorcompounds to prepare the polyols employed as Component A in the presentinvention include, for example, the lower alkylene oxides andsubstituted alkylene oxides such as ethylene oxide, 1,2-propylene oxide,1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, epibromohydrin,epiodohydrin, styrene oxide, mixtures thereof and the like.

Suitable polyoxyalkylene compounds which may be employed as the liquidmodifier compound (Component C) include, for example,

1. a liquid, totally-capped or non-hydroxyl-containing block or randomlyformed polyoxyalkylene glycol represented by the general formula##EQU1## wherein R and R' are independently selected from saturated andunsaturated hydrocarbon groups having from about 1 to about 6,preferably from about 1 to about 3, carbon atoms; R₁, R₂, . . . andR_(n) are independently hydrogen, an aryl group, an alkyl group orhaloalkyl group, said alkyl or haloalkyl group having from about 1 toabout 2 carbon atoms with the proviso that when R₁, R₂ . . . R_(n) is ahaloalkyl group, it is present in minor amounts i.e., a ratio of fromabout 0 to about 10 percent of the total R₁, R₂ . . . R_(n) groups, andx₁, x₂, . . . x_(n) are integers, such that the boiling point of theliquid capped polyalkylene glycol is above about 150°C;

2. a liquid partially capped, block or randomly formed polyoxyalkylenecompound represented by the general formula ##EQU2## wherein R and R₁,R₂ . . . R_(n) are as defined in formula I above and x₁, x₂, . . . x_(n)are integers, the sum of which provides the partially cappedpolyoxyalkylene compound with a molecular weight of at least about 700;

3. a liquid, block or randomly formed polyoxyalkylene glycol representedby the general formula ##EQU3## wherein R₁, R₂ . . . R_(n) are asdefined in formula I above and x₁, x₂ . . . x_(n) are integers, the sumof which provides the polyoxyalkylene glycol with an equivalent weightof at least about 700, and

4. a liquid, random or block polyoxyalkylene polyol having a hydroxylfunctionality of from 3 to about 8 represented by the general formula##EQU4## wherein R₁, R₂ . . . R_(n) are as defined in formula I above, Zis the residue of an initiator compound having from 3 to about 8hydroxyl groups, x₁, x₂, . . . x_(n) are integers, the sum of whichprovides the polyoxyalkylene polyol with a hydroxyl equivalent weight ofat least about 500 and q is an integer having a value of from 3 to about8.

Suitable ester-modified polyoxyalkylene compounds which may be employedas the liquid modifier compound (Component C) include, for example,those liquid ester-modified polyethers having a boiling point aboveabout 150°C represented by the general formula ##EQU5## wherein A is theresidue of an initiator or starting compound having from 1 to about 8hydroxyl groups, Z is the residue, excluding the carboxyl groups, of aninternal anhydride of a saturated or unsaturated acyclic aliphatic, asaturated or unsaturated cyclic aliphatic, or aromatic polycarboxylicacid, halogenated derivatives thereof and mixtures thereof, each R is asubstituent independently selected from hydrogen atoms, an alkyl radicalhaving from 1 to 20 carbon atoms, a halomethyl radical, a phenylradical, and a phenoxymethyl radical, an alkoxymethyl radical with theproviso that one of the R substituents must be hydrogen, R' is hydrogenor a saturated or unsaturated aliphatic group having from 1 to 20 carbonatoms, m has an average value of from about 1.0 to about 2.0, n has avalue from about 1 to about 5, x has a value from about 1 to about 8 andy has a value of 1 or 2 and wherein said ester-modified polyethercompound has a hydroxyl equivalent weight above about 500 when 3 or morehydroxyl groups are present and when 2 hydroxyl groups are present, anaverage equivalent weight of above about 700 and when zero or onehydroxyl group is present a molecular weight of above about 700.

Suitable initiators which may be employed to prepare the liquidpolyoxyalkylene and ester-modified polyoxyalkylene modifier compounds(Component C) of the present invention include compounds having from 1to about 8 hydroxyl groups such as, for example, methanol, ethanol,propanol, butanol, ethylene glycol, propylene glycol, butylene glycol,1,6-hexane diol, glycerine, trimethylolpropane, pentaerythritol,sorbitol, sucrose, mixtures thereof and the like.

When the liquid modifier compound, Component C, is an ester modifiedpolyether polyol, the initiator compound may also be and is preferablyan adduct of the above mentioned initiator compounds and one or more ofthe following vicinal epoxide-containing compounds, i.e., the initiatorcompound is a polyoxyalkylene compound having 1 to 8 hydroxyl groups,preferably 2 to about 3 or 4 hydroxyl groups.

Suitable vicinal epoxide compounds which may be reacted with the abovementioned initiator compounds to prepare the modifier compounds(Component C) employed in the present invention include, for example,ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butyleneoxide, epichlorohydrin, epibromohydrin, epiodohydrin, styrene oxide,mixtures thereof and the like.

The liquid modifier compounds represented by formulae I-IV and methodsfor their preparation are well known in the art, e.g. U.S. Pat. No.2,448,664; U.S. Pat. No. 2,425,755; U.S. Pat. No. 2,782,240 and U.S.Pat. No. 2,520,611. Methods for the preparation of the liquid modifiercompounds represented by the formula V are given in a copendingapplication Ser. No. 67,233, filed Aug. 26, 1970, now abandoned byRobert W. McAda, Jr. for "ESTER-MODIFIED POLYETHER POLYOLS" and in U.S.Pat. No. 3,502,601.

Suitable non-ester containing aromatic compounds which may be employedas the liquid modifier compound having a boiling point above about 150°C(Component C) in the present invention include, for example, straightand branch chain aliphatic, alkoxy and halogen substituted benzenes,aromatic substituted benzene and aromatic ethers, such as, for example,propenyl benzene, propylbenzene, butylbenzene, ethyltoluene,butyltoluene, propyltoluene, diphenyl oxide, biphenyl, o-, m- andp-diethylbenzene, dodecylbenzene, octadecylbenzene, bromobenzene,1-bromo-3-chlorobenzene, 1-bromo-4-fluorobenzene, 1-bromo-2-iodobenzene,1-bromo-3-iodobenzene, 1-chloro-4-fluorobenzene, o-dibromobenzene,m-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene,1,3-dipropoxybenzene, 1-ethyl-4-propylbenzene, 1-fluoro-4-iodobenzene,4-bromo-o-xylene, α-bromo-m-xylene, 4-bromo-m-xylene, α-chloro-m-xylene,4-ethyl-m-xylene, 5-ethyl-m-xylene, 2-bromo-p-xylene, α-chloro-p-xylene,2-ethyl-p-xylene, 2-ethyl-p-xylene, o-bromotoluene, m-bromotoluene, o-,m-, and p-chlorotoluene, tertiary butylstyrene, α-bromostyrene,β-bromostyrene, α-chlorostyrene, β-chlorostyrene, mixtures thereof andthe like.

The above compounds may be represented by the following general formulaprovided it is understood that such compounds represented by the formulaare liquids and have boiling points at atmospheric pressure above about150°C. ##SPC1##

wherein R₁, R₂ and R₃ are independently selected from an alkyl grouphaving from about 1 to about 18 carbon atoms, an alkenyl group havingfrom 2 to about 3 carbon atoms, a halogen, an alkoxy group, an aromaticgroup and hydrogen.

Other suitable aromatic compounds which may be employed as the liquidmodifier compound (Component C) in the present invention include liquidmulti-ring compounds having a boiling point above about 150°C such as,for example, 1-chloronaphthalene, 1-bromo-naphthalene, mixtures thereofand the like.

Suitable partially hydrogenated multi-ring aromatic compounds which maybe employed as the liquid modifier compound (Component C) in the presentinvention include, for example, 1,4-dihydronaphthalene,1,2,3,4-tetrahydronaphthalene, mixtures thereof and the like.

Suitable fatty acids and naturally occurring fatty oils which may beemployed as the liquid modifier compounds (Component C) in the presentinvention includes, for example, oleic acid, linoleic acid, linolenicacid, and the like. The fatty acids resulting from the hydrolysis ofnaturally occurring oils of animal and vegetable origin including forexample, linseed oil, castor oil, tung oil, fish oil, soya oil and thelike and such acids as are produced as byproducts in chemical processesincluding for example, tall oil, the byproduct resulting from theconversion of wood pulp to paper by the sulfate process, mixtures of anyof the above and the like.

Also operable as the liquid modifier compound are the naturallyoccurring fatty oils having boiling points above about 150°C including,for example, linseed oil, castor oil, tung oil, fish oil, soya oil, andthe like.

Suitable organophosphorus compounds which may be employed as the liquidmodifier compound, Component C, include, for example, organo phosphates,organo phosphites and organo phosphonates having boiling points aboveabout 150°C.

Organo phosphates, phosphites and phosphonates which may be employed asthe liquid modifier compound include those liquid compounds representedby the formulae ##EQU6## wherein R₁, R₂ and R₃ are independentlyselected from the group consisting of alkyl, alkoxyaryl, aryloxyaryl,alkaryl, aralkyl groups and halogen substituted derivatives thereof. Yis oxygen or sulfur, X is a halogen, i.e., chlorine, fluorine, bromineor iodine, n has a value of 1 or 2. Suitable such compounds include, forexample, tri-n-butyl phosphate, triethylphosphate, tricresylphosphate,tris-(beta-chloroethyl)phosphate, tris-(2,3-dibromopropyl)phosphate,butyl dichlorophosphate, 2-chloroethyl dichlorophosphate, ethyldichlorophosphate, diethyl fluorophosphate, bis(2-chloroethyl)fluorophosphate, dibutyl chlorophosphate, isoamyldichlorothionophosphate, ethyl dibromothiophosphate, 2-chlorophenyldichlorophosphate, 2-methoxyphenyl dichlorophosphate, 2-phenoxyphenyldichlorophosphate, 2-chloroethyl dichlorophosphite,tris(2-chloroethyl)phosphite, tributyl phosphite, tricresyl phosphite,triethyl phosphite, diethyl isoamylphosphonate, diethylethylphosphonate, dimethyl methylphosphonate, diethyl methylphosphonate,diisobutyl isobutylphosphonate, bis(2-bromopropyl)-2-bromopropanephosphonate.

When halo- or dihalo-phosphates or phosphites or their thionoderivatives are employed as the liquid modifier compound (component C),they are preferably added to the composition just prior to thenon-amine-containing catalyst so as to minimize their reaction with thehydroxyl groups of the polyol, component A.

The organo phosphorus compounds may be prepared by procedures describedin ORGANO-PHOSPHORUS COMPOUNDS, G. M. Kosolapoff, John Wiley & Sons,Inc., 1950.

Suitable liquid organic carbonates which may be employed as the liquidmodifier, component C, in the present invention include the acyclic andcyclic carbonates represented by the formulae ##EQU7## and ##EQU8##wherein each R₁. and R₂ are independently aryl, alkyl (having from about1 to about 6 carbon atoms) or alkenyl groups (having from about 1 toabout 6 carbon atoms) and substituted derivatives thereof and each R₃and R₄ are selected from the same groups as R₁ and R₂ and hydrogen.

Suitable liquid acyclic organic carbonates which may be employed in thepresent invention include, for example, bis(2-chloroethyl)carbonate,di-n-butyl carbonate, butyldiglycol carbonate, cresyldiglycol carbonate,dibutyl carbonate, di-2-ethylhexyl carbonate, dimethallyl carbonate,dinonyl carbonate and the like. The organic acyclic carbonate may beprepared by procedures given in U.S. Pat. No. 2,687,425.

Suitable liquid cyclic organic carbonates include, for example,propylene carbonate, butylene carbonate, styrene carbonate, mixturesthereof and the like. The cyclic organic carbonates may be prepared inthe manner described in Canadian Pat. No. 556,006.

Suitable cyclic polyethers which may be employed as the liquid modifier(component C) include, for example, the cyclic tetramer of ethyleneoxide, cyclic pentamer of propylene oxide, cyclic tetramer of propyleneoxide, mixtures of the above and mixtures of cyclic pentamers and aboveof ethylene oxide and or propylene oxide. Any liquid cyclic polyetherhaving a boiling point above 150°C may be employed as the liquidmodifier in the present invention including cyclic polyethers preparedfrom butylene oxide, epichlorohydrin and the like.

The liquid cyclic polyether modifier compounds may be prepared byprocedures mentioned in "Cyclic Polyethers and Their Complexes withMetal Salts" by C. J. Pedersen, J. Am. Chem. Soc., Vol. 89, p.7017-7036, 1968, "Twelve-Membered Polyether Rings. The Cyclic Tetramersof Some Olefin Oxides" by R. S. Kern; J. Org. Chem., Vol. 33, p.388-390, 1968; British Pat. Nos. 785,229 and 1,108,921.

Suitable halogenated aliphatic compounds having a boiling point aboveabout 150°C which may be employed as the modifier compound in thepresent invention include, for example, tetrabromoethane, bromoform,hexachlorobutadiene, tetrachlorobutadiene, 1,2,3,3-tetrachlorobutane,1,5-dibromo-pentane, 1,1,2-tribromopropane, 1,2,3-trichloropropene,polyepichlorohydrin diol having an equivalent weight above about 700 upto about 4000, chlorinated paraffins, e.g. "Chlorowax" No. 40,1-mercapto-3-chloropropanol-2, 3-chloropropane-1,2-diol,2-chloropropane-1,3-diol, 1,3-dichloro-2-propanol, mixtures thereof andthe like.

The halogenated aliphatic compounds which do not contain hydroxyl groupsmay be employed in quantities of from about 0.2 to about 50 percent byweight of the sum of the weights of components A, B and C, andpreferably from about 1 to about 10 percent by weight on the same basisi.e., the sum of the weights of components A, B and C. When thehalogenated aliphatic compounds employed herein also contain hydroxylgroups and have a hydroxyl equivalent weight of less than 500, thequantity which is to be employed is from about 0.2 to about 10 andpreferably from about 0.4 to about 5 percent by weight based upon thecombined weights of A, B and C.

Suitable cyclic sulfones which may be employed as the liquid modifiercompound include the 5-membered cyclic sulfones such as, for example,3-methylsulfolane (3-methyltetrahydrothiophene-1,1-dioxide) and thelike.

The term "liquid modifier boiling above about 150°C" includes eutecticmixtures of the previously described classes of compounds which aresolids at atmospheric pressure but said eutectic mixtures are a liquidat room temperature and atmospheric pressure which have boiling pointsabove about 150°C. Also included in the definition are those solidcompounds of the classes previously described which are dissolved in aliquid member of any of the described classes of compounds havingboiling points above about 150°C wherein the resultant solution is aliquid at standard conditions of temperature and pressure and haveboiling points at atmospheric pressure above about 150°C.

Suitable non-amine-containing catalysts for urethane formation include,for example, organo-metal compounds of tin, zinc, lead, mercury,cadmium, bismuth, cobalt, manganese, antimony, iron and the like suchas, for example, metal salts of a carboxylic acid having from about 2 toabout 20 carbon atoms including, for example, stannous octoate,dibutyltin dilaurate, dibutyltin diacetate, ferric acetylacetonate, leadoctoate, lead oleate, phenylmercuric propionate, cobalt naphthenate,lead naphthenate, mixtures thereof and the like.

It is preferred that the catalysts be employed in liquid form. Thosecatalysts which are not ordinarily liquids may be added as a solution ina solvent which is compatible with the other components employed in thecomposition of the present invention. Suitable such solvents include,for example, dioctylphthalate, polyoxyalkylene glycols, mineral spirits,dipropylene glycol, mixtures thereof and the like.

It has previously been stated that the quantity of thenon-amine-containing catalyst is in the range of from about 0.2 to about10%. However, when the liquid modifier compound is anon-ester-containing aromatic compound or a halogenated aliphaticcompound as described herein, the operable range for the quantity of thecatalyst to be employed is from about 0.01 to about 10% and preferablyfrom about .05 to about 2% and most preferably from about 0.1 to about0.5% by weight based upon the combined weights of Components A, B and C.

Suitable polyisocyanates which may be employed as Component B in thecompositions of the present invention include, for example, any organicpolyisocyanate having 2 or more NCO groups per molecule and no othersubstituents capable of reacting with the hydroxyl groups of thepolyoxyalkylene compound. Suitable such polyisocyanates include, forexample, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, hexamethylenediisocyanate, p,p'-diphenylmethanediisocyanate, p-phenylenediisocyanate,hydrogenated methylene diphenyldiisocyanate (e.g. Hylene W) naphthalenediisocyanate, dianisidine diisocyanate, polymethylenepolyphenyl-isocyanate, mixtures of one or more polyisocyanates and thelike.

Other organic isocyanates which may suitably be employed and which areto be included in the term organic polyisocyanate include isocyanateterminated prepolymers prepared from the previously mentioned polyolsand the above mentioned isocyanates.

The cured compositions of the present invention vary from transparentsolids to white or off-white opaque solids, depending upon theparticular liquid modifier compound (component C) and/or polyisocyanate(component B) employed to produce such compositions.

Suitable modifier compounds which may be employed to produce solidopaque products include, for example,

1. those compounds represented by formula I wherein at least 20% byweight of the compound is derived from units wherein R₁, R₂ . . . R_(n)are hydrogen.

2. those compounds represented by formula II wherein the molecularweight is at least about 1500;

3. those compounds represented by formula III wherein the molecularweight is at least about 3000; and

4. those compounds represented by formula IV wherein the molecularweight is at least about 7000 and at least 20% of the molecular weightis derived from units wherein R₁, R₂, . . . R_(n) are hydrogen.

Suitable modifier compounds which may be employed to produce transparentsolid products include, for example,

1. those compounds represented by formula I wherein less than about 20%by weight of the compound is derived from units wherein R₁, R₂, . . .R_(n) are hydrogen;

2. those compounds represented by formula II wherein the molecularweight is greater than about 700 but less than about 1500 and whereinless than 207 of the molecular weight is derived from units wherein R₁,R₂, . . . R_(n) are hydrogen;

3. those compounds represented by formula III wherein the molecularweight is greater than about 700 and less than about 3000 and whereinless than about 20% of the molecular weight is derived from unitswherein R₁, R₂, . . . R_(n) are hydrogen; and

4. those compounds represented by formula IV having a molecular weightfrom about 1500 to less than about 7000 and wherein less than about 20%of the molecular weight is derived from units wherein R₁, R₂, . . .R_(n) are hydrogen.

Rigid polyurethane products can be prepared by rapidly mixing thecomponents of the compositions of the present invention. It is preferredto thoroughly blend together the components represented by A, thepolyol, B, the polyisocyanate and C, the liquid modifier compound andthen mixing the resultant mixture with Component D, the catalyst.Mechanical dispensing or combination mixing-dispensing devices can beemployed by utilizing 2 or more streams of the individual components ormixtures of the components which are introduced into said device.

Other components including inert fillers such as, for example, sand,microballoons, glass fibers, asbestos, aluminum granules, siliconcarbide powder and the like, coloring agents, such as pigments and dyesincluding, for example, chromic oxide, ferric oxide, mixtures thereofand the like may be employed in the compositions of the presentinvention without detracting from the scope thereof.

The compositions of the present invention rapidly produce solid productswhich may be demolded, i.e., the articles produced therefrom may beremoved from the mold, within about 5 minutes, usually within about 3minutes and preferably within about 1 minute or less from the time thecatalyst is blended into the mixture and do not require the applicationof external sources of heat to accomplish this, although in somecircumstances it may be desirable to post cure, at elevatedtemperatures, the products in order to develop certain properties. Thecompositions of the present invention not only can be demolded within 5minutes and often in less than 2 to 3 minutes, but the cast objectsproduced therefrom have developed sufficient strength properties to beemployed immediately upon cooling to room temperature for their intendedpurpose. The cast objects are hot or warm to the touch immediately afterremoving from the mold due to the exotherm generated during thereaction. This is a valuable contribution to the urethane molding art,in that productivity can be increased employing a given quantity ofmolds.

The choice of the catalyst involves the desired time delay between thecatalyst being mixed into the reagents and the liquid mix "instantly"solidifying. For example, if tolylene diisocyanate is used along with apolyol that is the reaction product of glycerine with propylene oxideand having a molecular weight of about 260 plus a polyoxypropyleneglycol having a molecular weight of about 4000 as the liquid modifiercompound, then the addition of about 1% stannous octoate catalyst willyield a delay or induction time of about 10 seconds before the mixturesuddenly "freezes" into a solid. Substitution of dibutyltin dilaurate atthe same catalyst level stretches this delay time to about 20 seconds,and phenyl mercuric propionate exhibits a delay time of about 120seconds before extremely rapid solidification occurs.

The change of isocyanate to a less reactive one, i.e., the substitutionof hexamethylene diisocyanate for tolylene diisocyanate, correspondinglyincreases the delay time before rapid solidification takes place.

Suitable materials from which adequate molds, for casting thecompositions of the present invention, may be prepared include polymerssuch as, for example, polyethylene, polypropylene, their copolymers andthe like, polyurethanes, polysiloxane elastomers, Mylar, curedpolyepoxides, mixtures thereof and the like.

It is preferred to employ relatively thin wall molds or molds having alow heat capacity or thermal conductivity. Heavy molds made ofrelatively high thermal conductivity materials such as aluminum, copper,iron or steel and the like may present curing problems, i.e., thereactants may not be readily demolded unless the mold is preheated toabout 50°-90°C, especially when casting relatively thin sections.However, high thermal conductivity materials such as copper or aluminumcan be employed as thin wall molds without preheating if the thermalcapacity of the mold is relatively low compared to the amount of heatliberated in the casting.

The compositions of the present invention are useful as, but notrestricted to such uses as, a casting material for preparing bearingsurfaces, annular spacers, decorative objects, furniture or furniturecomponents, gears or other machine components, threaded protective plugsand caps, and the like.

The following examples are illustrative of the present invention but arenot to be construed as to limiting the scope thereof in any manner.

The following examples 1-10 are illustrative of solid, rigid, opaque andtranslucent products.

EXAMPLE 1 A. An Example of the Present Invention

In a suitable container were thoroughly blended 30 grams of VoranolCP-260 (the reaction product of glycerine with propylene oxide having amolecular weight of about 260) as the polyol, 30 grams of P-4000, apolyoxypropylene glycol having a molecular weight of about 4000, as theliquid modifier compound and 30 grams of Hylene TM (an 80/20 mixture byweight of the 2,4-and 2,6-isomers of tolylene diisocyanate having an NCOequivalent weight of about 87).

After the above components were well mixed, 1 cc of a liquid dibutyltindilaurate, commercially available as T-12 catalyst from Metal andThermit Corp., was rapidly stirred in and the resultant mixture waspoured into a polyethylene beaker. Thirty seconds after stirring in thecatalyst, the mixture suddenly turned an opaque white color andunderwent substantially instantaneous hardening. Sixty seconds after thecatalyst was added, a rigid, hard, white, opaque polymer casting wasdemolded, i.e., removed from the polyethylene beaker, and was found tohave a density of 1.055 grams/cc.

B. Comparative Demonstration -- Effect of One-Tenth the Amount ofCatalyst

The same procedure and composition as in A above was employed exceptthat 0.1 cc of the dibutyltin dilaurate catalyst was employed with thefollowing results.

60 seconds after the catalyst was added, the mixture was still atransparent liquid.

120 seconds after the catalyst was added, the mixture was an opaqueliquid.

180 seconds after the catalyst was added, the mixture hardened but wastoo tacky to be demolded.

400 seconds after the catalyst was added, the casting was demolded.

The product was found to be a warped, rigid, white, opaque solid thatwas filled with gross bubbles or gas cells. This casting had a densityof 0.864 grams/cc.

C. Comparative Demonstration of Effect of Omitting the Liquid Modifier

Same procedure as in A above employing 33 grams of the indicated polyoland 33 grams of the polyisocyanate. The mixture suddenly gelled afterthe catalyst addition; however within the next 4 minute interval, thecast polymer grossly swelled and generated copious quantities ofinternal gas bubbles and open fissures across the top surface of thecasting. The cured polymer mass had a density of 0.56 grams/cc.

EXAMPLES EMPLOYING VARIOUS POLYISOCYANATES EXAMPLE 2

Same procedure as in Example 1A employing the following components:

33 grams of Voranol CP-260 as the polyol

33 grams of P4000 as the liquid modifier

50 grams of Isonate 143L (dimerized diphenylmethanediisocyanate havingan NCO equivalent weight of about 144 and a functionality of about 2.25)

1 cc lead octoate containing 24% Pb.

In less than 15 seconds after catalyst addition, the mixture suddenlysolidified into a cream-colored, opaque, hard, rigid polymer which wasdemoldable within 40 seconds.

EXAMPLE 3

Same procedure as in Example 1A employing the following components:

30 grams of Voranol CP-260

30 grams of P-3000 (a polyoxypropylene glycol having an averagemolecular weight of about 3000) as the liquid modifier

45 grams of Hylene W (hydrogenated methylene diphenyldiisocyanate havingan NCO equivalent weight of about 132 and a functionality of about 2).

1 cc of lead octoate having 24% Pb.

The mixture suddenly turned into an opaque, dense, hard solid withinabout 15 seconds and could be demolded within about 40 seconds.

EXAMPLE 4

Same procedure as in Example 1A employing the following components.

30 grams of Voranol CP-260

30 grams of P-3000

32 grams of Takenate 500 (Xylylene diisocyanate having an NCO equivalentweight of about 94 and an average functionality of about 2).

1 cc of lead octoate (24% Pb).

The mixture suddenly turned into an opaque, white solid within about 30seconds and could be demolded within about 50 seconds.

EXAMPLES EMPLOYING VARIOUS POLYOLS EXAMPLE 5

Same procedure as in Example 1A employing the following components.

26 grams of Voranol CP450 (reaction product of glycerine with propyleneoxide having a molecular weight of about 450).

15 grams of P-4000

16 grams of Hylene TM

1 cc of lead octoate (24% Pb)

The mixture rapidly set to produce a rigid, hard, opaque, white, solid,casting within about 25 seconds which could be demolded within about 40seconds.

EXAMPLE 6

Same procedure as in Example 1A employing the following components.

30 grams of the reaction product of glycerine with ethylene oxide in amolar ratio of 1:3 and having a hydroxyl equivalent weight of about75.9.

30 grams P-4000

30 grams Hylene TM

1 cc lead octoate (24% Pb)

The mixture suddenly set into a hard, rigid, white, opaque solid productwithin about 30 seconds which could be demolded within about 50 seconds.

COMPARATIVE EXAMPLE 6A

To demonstrate that initiator compounds having a functionality of 3 butwhich have not been reacted with an alkylene oxide cannot be employed asthe polyol to produce the compositions of the present invention, Example6 was duplicated by substituting glycerine and again substitutingtrimethylol propane as the polyol component i.e., as a replacement forthe glycerine-ethylene oxide reaction product.

In both instances, the formulations did not demonstrate an "instant set"capability and they could not be demolded within 10 minutes aftercasting. After several hours, these castings were found to be lowstrength foams.

EXAMPLES OF VARIOUS LIQUID POLYOXYALKYLENE MODIFIER COMPOUNDS EXAMPLE 7

Same procedure as in Example 1A employing the following composition.

33 grams of Voranol CP-260

33 grams of the reaction product of allyl alcohol with a 50-50 wt. %mixture of propylene oxide and ethylene oxide having a molecular weightof about 1800 and finally end capped with a methyl group, as the liquidmodifier.

33 grams of Hylene TM

1 cc of lead octoate (24% Pb).

The mixture set into a rigid, hard, white, opaque solid having a densityof about 1.12 grams/cc within about 20 seconds which could be demoldedwithin about 40 seconds.

EXAMPLE 8

Same procedure as in Example 1A employing the following composition.

33 grams of Voranol CP-260

33 grams of the adduct of propylene oxide onto butanol and having amolecular weight of about 2000.

33 grams of Hylene Tm

1 cc of lead octoate (24% Pb).

The mixture set into a rigid, white, opaque, solid product within about20 seconds which could be demolded within about 40 seconds.

EXAMPLE 9

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

32 grams of the adduct of 80-20 mole percent mixture of propylene oxideand ethylene oxide onto a glycerine-propylene oxide adduct having amolecular weight of about 260, the molecular weight of the resultantproduct being about 10,000.

30 grams of Hylene TM

1 cc of lead octoate (24% Pb)

The mixture rapidly set into an opaque, white, hard, solid productwithin about 20 seconds and could be demolded within about 40 seconds.

EXAMPLE 10

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of propylene glycol initiated polyepichlorohydrin having anaverage molecular weight of about 2000.

30 grams Hylene TM

1 cc of lead octoate (24% Pb)

The composition rapidly set into a hard, opaque, rigid, solid productwithin about 20 seconds which was readily demoldable within about 40seconds.

The following examples 11-19 are illustrative of solid, rigid,transparent products.

EXAMPLE 11

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of Voranol CP-4701 (the reaction product of glycerine withpropylene oxide end-capped with ethylene oxide and having an averagemolecular weight of about 4700)

30 grams of Hylene TM

1 cc lead octoate

The mixture instantly set into a rigid, transparent, solid productwithin about 20 seconds and could be demolded within about 30 seconds.The casting had a density of 1.1 grams/cc.

EXAMPLES OF VARIOUS POLYISOCYANATES, POLYOLS AND MODIFIER COMPOUNDSEXAMPLE 12

Same procedure as in Example 1A employing the following composition.

33 grams of Voranol CP-260

33 grams of Voranol CP-3000 (glycerine initiated polyoxypropylene glycolhaving an average molecular weight of about 3000).

50 grams Isonate 143L

1 cc T-9 catalyst (stannous octoate commercially available from Metaland Thermit Corp.).

The mixture rapidly set into a rigid, transparent, solid within about 15seconds and could be demolded within about 30 seconds.

EXAMPLE 13

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of Voranol CP-1500 (glycerine initiated polyoxypropylene glycolhaving an average molecular weight of about 1500)

30 grams of Hylene TM

1 cc of T-9 catalyst

The mixture instantly set into a transparent, solid product within about40 seconds and could be demolded within about 60 seconds.

COMPARATIVE EXAMPLE 13-A

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of Voranol CP-700 (glycerine initiated polyoxypropyleneglycolhaving an average molecular weight of about 700)

30 grams of Hylene TM

1 cc T-9 catalyst

The mixture demonstrated instant set characteristics but the productswelled and cracked.

EXAMPLE 14

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

31 grams of a triol prepared by reacting glycerine with a mixture ofpropylene oxide and ethylene oxide having an average molecular weight ofabout 4100 and about 16 weight percent ethylene oxide).

30 grams Hylene TM

1 cc lead octoate (24% lead)

The mixture instantly set within about 30 seconds and the rigid, solid,clear casting was demolded within about 50 seconds.

EXAMPLE 15

Same procedure as in Example 1A employing the following composition.

30 grams of the reaction product of glycerine with propylene oxide in amolar ratio of about 1:3 respectively.

30 grams Voranol CP-4701 (glycerine initiated polyoxypropylene glycolend-capped with ethylene oxide)

45 grams Hylene W

1 cc lead octoate (24% Pb)

At the end of 180 seconds the mixture was still liquid; at 195 secondsthe mixture began to gel rapidly, and at 210 seconds the casting was arigid transparent tack-free solid.

When the same formulation was catalyzed by 5 cc of 24% Pb octoate, thesolidification was not greatly accelerated, e.g. the mix was stillliquid at 120 seconds, gelling occurred rapidly at 135 seconds, and theproduct was a transparent rigid solid at 150 seconds after catalystaddition.

EXAMPLE 16

Same procedure as in Example 1A employing the following composition.

30 grams of the reaction product of glycerine with propylene oxide at amolar ratio of 1:3 respectively.

30 grams of Voranol CP-4701

30 grams of hexamethylene diisocyanate

1 cc of lead octoate (24% Pb)

The mixture set into a transparent, rigid, solid within about 70 secondsand could be demolded within about 90 seconds.

EXAMPLE 17

Same procedure as in Example 1A employing the following composition.

26 grams of Voranol CP-450 (glycerine initiated polyoxypropylene glycolhaving an average molecular weight of about 450).

15 grams of Voranol CP-4701

16 grams of xylylene diisocyanate

0.7 cc of lead octoate (24% Pb)

The mixture instantly set into a transparent, rigid, solid productwithin about 30 seconds which could be demolded within about 50 seconds.

EXAMPLE 18

Same procedure as in Example 1A employing the following composition.

33 grams of Voranol CP-260

33 grams of a butanol initiated polyoxypropylene glycol having anaverage molecular weight of about 1000.

33 grams of Hylene TM

1 cc of lead octoate catalyst

The mixture instantly set into a transparent, rigid, dense productwithin about 20 seconds and could be demolded within about 35 seconds.

EXAMPLE 19

Same procedure as in Example 1A employing the following composition.

33 grams of Voranol CP-260

30 grams of a polyoxypropylene glycol having an average molecular weightof about 1000.

35 grams of Hylene TM

1 cc of lead octoate (24% Pb)

The mixture instantly set into a transparent, rigid, dense productwithin about 10 seconds and could be demolded within about 30 seconds.

EXAMPLE 20

Same procedure as in Example 1A employing the following components:

35 grams of Voranol CP260

30 grams of distilled tall oil

35 grams of Hylene TM

1 cc of stannous octoate (T-9)

about 30 seconds after catalyst addition, the liquid reactants suddenlysolidified into an opaque, off-white, rigid, solid having a density of1.15 grams/cc.

EXAMPLE 21

33 grams of Voranol CP-260

30 grams of distilled Tall oil

45 grams of PAPI (polymethylenepolyphenylisocyanate having an averagefunctionality of about 2.6 and an NCO equivalent weight of about 133)

1 cc T-9 catalyst

About 35 seconds after catalyst addition, the mixture suddenly "froze"into a rigid, solid material having a density of 1.04 grams/cc.

EXAMPLE 22

Same procedure as in Example 1A employing the following components:

30 grams of the reaction product of pentaerythritol with propylene oxidein a molar ratio of 1 to 5 respectively.

30 grams of linseed oil

30 grams of toluene diisocyanate

1 cc of T-9 catalyst

The mixture suddenly set into a dense, solid product.

EXAMPLE 23

Same procedure as in Example 1A employing the following components:

33 grams of the reaction product of pentaerythritol with propylene oxidein a molar ratio of 1 to 5 respectively.

30 grams of distilled tall oil

33 grams of toluene diisocyanate

1 cc of T-9 catalyst

The mixture solidified within about 30 seconds after catalyst additionand was demolded after about 45 seconds after catalyst addition. Therigid, solid casting had a density of 1.11 grams/cc.

EXAMPLE 24

Same procedure as in Example 1A employing the following components:

30 grams of Voranol CP-260

20 grams of oleic acid

46 grams of PAPI (polymethylene polyphenylisocyanate)

1 cc of T-9 catalyst

About 35 seconds after catalyst addition, the mixture suddenly set intoa rigid, light brown casting which had a density of about 1.04 grams/cc.

EXAMPLE 25

Same procedure as in Example 1A employing the following components:

30 grams of the reaction product of glycerine with propylene oxide to amolecular weight of about 260.

20 grams of linseed oil

46 grams of PAPI

1 cc of T-9 catalyst

The mixture suddenly set into a rigid, khaki-colored, opaque, solidwithin about 25 seconds after catalyst addition. The casting wasdemolded within about 1 minute after catalyst addition and had a densityof 1.12 grams/cc.

EXAMPLE 26

Same procedure as in Example 1A employing the following components.

30 grams of the reaction product of glycerine with propylene oxide to amolecular weight of about 260.

20 grams of castor oil

46 grams of PAPI

1 cc of T-9 catalyst

About 25 seconds after catalyst addition, the mixture set into a rigid,solid which was demolded in about 1 minute after catalyst addition. Thecasting had a density of 1.12 grams/cc.

EXAMPLE 27

Same procedure as in Example 1A employing the following components:

30 grams of Voranol CP-260

30 grams of Hylene TM

30 grams of 1,2,3,4-tetrahydronaphthalene

1 cc of lead octoate (24% Pb)

About 15 seconds after catalyst addition, the mixture suddenly set intoa rigid, clear, transparent, solid.

EXAMPLE 28

Same procedure as in Example 1A employing the following components:

30 grams of the reaction product of glycerine with propylene oxide at amole ratio of about 1 to 3 respectively and having a molecular weight ofabout 260.

45 grams PAPI

20 grams acetophenone

1 cc T-9 catalyst

The mixture was cast into a shallow Mylar tray and suddenly solidifiedwithin about 20 seconds after catalyst addition and the cast sheet wasremoved about 35 seconds later. The product had the followingproperties:Density >1 gram/ccShore D Hardness about 92

EXAMPLE 29

Same procedure as in Example 1A employing the following components:

30 grams reaction product of glycerine with propylene oxide to amolecular weight of about 260.

30 grams of 1,2,4-trichlorobenzene

30 grams toluenediisocyanate

1 cc lead octoate

About 15 seconds after catalyst addition, the mixture suddenly set intoa rigid, transparent solid.

EXAMPLE 30

Same procedure as in Example 1A employing the following components:

35 grams of the reaction product of glycerine with propylene oxide to amolecular weight of about 260.

20 grams of 1,2,3,4-tetrahydronaphthalene

10 grams of 1,2,4-trichlorobenzene

35 grams of toluene diisocyanate

0.3 cc of lead octoate

The mixture suddenly set into a rigid, transparent solid.

EXAMPLE 31

Same procedure as in Example 1A employing the following components;

30 grams of the reaction product of glycerine with propylene oxide to amolecular weight of about 260.

30 grams of α-chloronaphthalene

30 grams of toluenediisocyanate

0.4 cc of lead octoate

About 20 seconds after catalyst addition, the mixture suddenly set intoa rigid, transparent solid.

EXAMPLE 32

A. Same procedure as in Example 1A employing the following components:

30 grams of the reaction product of glycerine with propylene oxide to amolecular weight of about 260.

30 grams of 1,2,4-triethylbenzene (b.p. approx. 215°C)

30 grams of toluenediisocyanate

0.4 cc of lead octoate

About 30 seconds after catalyst addition, the mixture suddenly set intoa rigid, opaque solid. About 45 seconds after catalyst addition, thecasting was demolded and had a density of 1.12 grams/cc.

B. Comparative Example -- Use of Modifier Compound With a Boiling PointBelow About 150°C.

Same procedure as in Example 1A employing the following components:

30 grams of the reaction product of glycerine with propylene oxide to amolecular weight of about 260.

30 grams of ethylbenzene (b.p. approx. 136°C)

30 grams of toluene diisocyanate

0.4 cc of lead octoate

About 20 seconds after catalyst addition, the mixture suddenly swelledwith gross bubble formation to yield an expanded rigid casting having anapparent density of 0.67 grams/cc.

EXAMPLE 33

Same procedure as in Example 1-A employing the following composition:

30 grams of the reaction product of glycerine with about 3 moles ofethylene oxide per mole of glycerine

32 grams xylylene diisocyanate

30 grams tris(2-chloroethyl)phosphate

0.5 cc lead octoate

The mixture instantaneously set within about 15 seconds after catalystaddition and was demolded within about 30 seconds after catalystaddition thereby producing a clear, transparent, rigid, non-brittlesolid casting having a density of about 1.25 grams/cc.

EXAMPLE 34

Same procedure as in Example 1-A employing the following composition:

30 grams of the reaction product of glycerine with 3 moles of propyleneoxide per mole of glycerine having a hydroxyl equivalent weight of about87.

46 grams PAPI (polymethylene polyphenylisocyanate)

20 grams tri-n-butylphosphate

1 cc stannous octoate catalyst

The mixture suddenly solidified within about 20 seconds after catalystaddition and the resultant casting was demolded within about 30 secondsafter catalyst addition. The product was a tough, dark colored(transparent in very thin sections) solid, rigid product having adensity of 1.15 grams/cc.

EXAMPLE 35

Same procedure as in Example 1A employing the following composition.

30 grams Voranol CP-260

30 grams toluenediisocyanate

30 grams tricresyl phosphate

0.5 cc lead octoate (24% lead)

The mixture was cast as a sheet and within about 10 seconds aftercatalyst addition, suddenly solidified into a tough, colorless,transparent rigid solid.

EXAMPLE 36

Same procedure as in Example 1A employing the following composition:

30 grams of the reaction product of glycerine with propylene oxide in amolar ratio of about 1:3 having a hydroxyl equivalent weight of 87.

30 grams of toluene diisocyanate

30 grams of triethylphosphate

0.5 cc. of lead octoate

The mixture was cast as a sheet which instantly set into a transparent,relatively soft sheet having an elongation less than about 100 percent.The relative softness of this product is believed to have been derivedfrom a side effect of the triethylphosphate also functioning as aplasticizer at this concentration.

EXAMPLE 37

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of toluene diisocyanate

30 grams of tributylphosphite

0.5 cc of lead octoate

The mixture suddenly solidified into an opaque, white, rigid castingwithin about 10 seconds after catalyst addition.

EXAMPLE 38

Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of toluene diisocyanate

30 grams of bis(2-bromopropyl)2-bromopropane phosphonate

1 cc of stannous octoate (T-9)

the mixture suddenly solidified into a transparent, solid, rigid castingwithin about 20 seconds after catalyst addition and was demolded withinabout 40 seconds after catalyst addition.

EXAMPLE 39

Same procedure as in Example 1A employing the following composition.

45 grams of Voranol CP-260

30 grams of tris(2-chloroethyl)phosphate

75 grams of ISONATE 143L (a diphenylmethane diisocyanate which has beendimerized with phosphoric acid and having an NCO equivalent weight ofabout 144 and an average functionality of about 2.25)

1 cc of dibutyl tin dilaurate

The above mixture was cast onto a Mylar sheet and suddenly solidifiedwithin about 20 seconds after catalyst addition and within about 40seconds after catalyst addition a rigid, yellow-brown, transparent sheetwas removed from the casting surface.

Test specimens cut from the above prepared sheet had the followingproperties.

    ______________________________________                                        tensile strength (ultimate)                                                                         7500 psi                                                % elongation          10                                                      Hardness, Shore D     90                                                      ______________________________________                                    

EXAMPLE 40

Same procedure as in Example 1-A employing the following composition:

30 grams of the reaction product of glycerine with ethylene oxide in amolar ratio of 1:3 having a hydroxyl weight of 75.9.

30 grams of propylene carbonate

30 grams of toluene diisocyanate (80% 2,4- and 20% 2,6-isomer mixture)

0.5 cc of lead octoate

The mixture instantly set within about 10 seconds after catalystaddition into rigid, transparent casting having a density greater than 1gram/cc.

EXAMPLE 41

Same procedure as in Example 1-A employing the following composition:

30 grams of Voranol CP-260

20 grams of bis(2-chloroethyl)carbonate

20 grams of toluene diisocyanate

0.5 cc of stannous octoate

The mixture suddenly solidified within about 10 seconds after catalystaddition which was demolded within about 20 seconds after catalystaddition thereby producing a transparent, rigid dense casting.

EXAMPLE 42

Same procedure as in Example 1-A employing the following composition:

45 grams of Voranol CP-260

30 grams of propylene carbonate

69 grams of polymethylene polyphenylisocyanate

1 cc of stannous octoate

The above mixture was cast onto a Mylar sheet which instantly set withinabout 20 seconds after catalyst addition.

The dark brown, rigid, transparent product was removed from the Mylarcasting surface within about 45 seconds after catalyst addition. Theproduct was found to possess the following properties.

    ______________________________________                                        tensile strength      4940 psi                                                elongation            12%                                                     Hardness, Shore D     87                                                      ______________________________________                                    

EXAMPLE 43

Same procedure as in Example 1-A employing the following composition:

30 grams of the reaction product of glycerine with ethylene oxide in amolar ratio of 1:3 respectively having a hydroxyl equivalent weight ofabout 75.9.

32 grams of xylylene diisocyanate

30 grams of the cyclic tetramer of ethylene oxide

0.5 cc of lead octoate (24% Pb)

The mixture suddenly solidified within about 15 seconds after catalystaddition and the casting was demolded within about 25 seconds aftercatalyst addition. The casting was a transparent rigid solid which had adensity of 1.2 grams/cc.

EXAMPLE 44

Same procedure as in Example 1-A employing the following composition

30 grams of Voranol CP-260

30 grams of toluene diisocyanate

30 grams of a mixture of cyclic polyethers of propylene oxide containingpentamer and higher homologs.

1 cc of lead octoate.

The mixture suddenly solidified within about 12 seconds after catalystaddition and the solid product was demolded within about 30 secondsafter catalyst addition yielding a translucent, rigid off-white castinghaving a density of 1.15 grams/cc.

EXAMPLE 45

Same procedure as in Example 1-A employing the following composition.

30 grams of the reaction product of pentaerythritol with propylene oxidein a molar ratio of about 1:5 respectively and having a molecular weightof about 415-430.

46 grams of PAPI (polymethylene polyphenylisocyanate)

30 grams of the cyclic tetramer of propylene oxide.

1 cc of stannous octoate (T-9).

the composition suddenly set within about 25 seconds after catalystaddition to yield a dark, rigid casting having a density of 1.09grams/cc which was readily demolded within 40 seconds after catalystaddition.

EXAMPLE 46

Same procedure as in Example 1-A employing the following composition:

32 grams of Voranol CP-260

32 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

3 grams of "Chlorowax" No. 40 (a liquid chlorinated paraffin having aspecific gravity of 1.15, a viscosity of 25 poises at 25°C, manufacturedand sold by Diamond-Shamrock Chemicals)

0.5 cc of lead octoate

The mass suddenly set, within about 10 seconds after catalyst addition,into a rigid casting having a density of 1.2 grams/cc and had no visualindications of cracks, distortions or bubble formation.

EXAMPLE 47

Same procedure as in Example 1-A employing the following composition:

30 grams of Voranol CP-260

25 grams of 1,2,3-trichloropropane

45 grams of PAPI (a polymethylene polyphenyl isocyanate having anaverage functionality of about 2.6-2.8 and an NCO equivalent weight ofabout 134).

1 cc of stannous octoate (T-9 commercially available from M & TChemicals).

The mixture suddenly solidified within about 30 seconds after catalystaddition and 15 seconds later was demolded. The dark, dense, rigidcasting had a density of 1.2 g/cc.

EXAMPLE 48

Same procedure as in Example 1-A employing the following composition:

30 grams of Voranol CP-260

30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

0.5 cc of lead octoate (24% lead)

20 grams tetrabromoethane

The blend suddenly solidified within about 15 seconds after catalystaddition and was demolded within about 30 seconds after catalystaddition thereby producing a dense, rigid, bubble-free casting having adensity of 1.58 grams/cc.

EXAMPLE 49

Same procedure as in Example 1-A employing the following composition.

37 grams of Voranol CP-260

37 grams of toluene diisocyanate (80/20 blend of 2,4- and 2,6-isomers)

3 grams of tetrabromethane

0.5 cc of lead octoate (24% lead)

The mixture suddenly set within about 15 seconds after catalyst additionto yield a dense rigid, bubble-free casting.

EXAMPLE 50

Same procedure as in Example 1-A employing the following composition.

30 grams of Voranol CP-260

30 grams of TDI (80/20 mixture of 2,4- and 2,6-isomers)

25 grams of 1,10-dibromodecane

0.5 cc of lead octoate

The mixture suddenly solidified within about 15 seconds after catalystaddition and was demolded within about 30 seconds after catalystaddition to provide a dense, rigid, bubble- and crack-free castinghaving a density of 1.35 grams/cc.

EXAMPLE 51

Same procedure as in Example 1-A employing the following composition.

30 grams of Voranol CP-260

30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

30 grams of bromoform

0.5 cc of lead octoate

The mixture solidified within about 15 seconds providing a dense, rigid,bubble-free casting.

EXAMPLE 52

Same procedure as in Example 1-A employing the following composition.

30 grams of Voranol CP-260

30 grams of hexachlorobutadiene

30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

1 cc of lead octoate

The mixture solidified to within 15 seconds after catalyst addition toprovide a dense, rigid, bubble-free casting.

EXAMPLE 53

Same procedure as in Example 1-A employing the following composition.

32 grams of Voranol CP-260

32 grams of toluenediisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

4 grams of polyepichlorohydrin diol* having a molecular weight of about2000 0.5 cc of lead octoate

This mixture rapidly set into a dense, rigid casting having a density of1.2 grams/cc.

EXAMPLE 54

Same procedure as in Example 1-A employing the following composition:

40 grams of Voranol CP-260

40 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

40 grams of "Chlorowax" No. 40

0.5 cc of lead octoate

The mixture rapidly solidified thereby forming a dense, rigid castinghaving a density greater than 1 gram/cc.

EXAMPLE 55 (COMPARATIVE)

This comparative example illustrates the inoperability of halogenatedaliphatic compounds having a boiling point below 150°C. Same procedureas in Example 1-A employing the following composition:

30 grams of Voranol CP-260

30 grams of perchloroethylene (boiling point = 121°C)

30 grams of toluenediisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

0.8 cc of lead octoate

The above mixture suddenly expanded within about 15 seconds aftercatalyst addition into a non-uniform cellular rigid mass having adensity of 0.48 gram/cc.

EXAMPLE 56

Same procedure as in Example 1-A employing the following composition:

30 grams of Voranol CP-260

30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

40 grams of α-chloronaphthalene

0,05 cc of lead octoate (24% lead)

The mixture suddenly solidified about 65 seconds after catalyst additionto yield a transparent rigid polymer which was demolded about 90 secondsafter catalyst addition. The density of this casting was found to be1.17 grams/cc.

EXAMPLE 57

Same procedure as in Example 1-A employing the following composition:

30 grams of Voranol CP-260

30 grams of toluene diisocyanate (80/20 mixture)

15 grams of Voranol CP-1500

15 grams of triethylbenzene

0.05 cc of lead octoate (24% lead)

This blend was cast into a polyethylene mold and the blend suddenlysolidified about 50 seconds after catalyst addition and was removed fromthe mold 75 seconds after catalyst addition. This transparent rigidcasting was found to have a density of 1.16 grams/cc.

EXAMPLE 58

Same procedure as in Example 1A employing the following composition:

30 grams of Voranol RS-350, a commercially available 8-functionalpolyether polyol having an OH equivalent weight of about 174

15 grams of Voranol CP-260

30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomer)

30 grams of triethylbenzene

0.1 cc of lead octoate

This blend solidified into a dense opaque, rigid casting about 35seconds after catalyst addition; the casting was removed from the mold20 seconds later to yield an opaque polymer having a density of1.082/cc.

EXAMPLE 59

Same procedure as in Example 1-A employing the following composition:

60 grams of Voranol RS-350

30 grams of toluene diisocyanate (80/20 mixture)

30 grams of trichlorobenzene

1 cc of lead octoate (24% lead)

This blend was cast into a polyethylene mold and was found to solidifyabout 15 seconds after catalyst addition; the casting was removed fromthe mold 25 seconds after catalyst addition.

EXAMPLE 60

Same procedure as in Example 1-A employing the following composition:

130 grams of Voranol CP-260

130 grams of toluenediisocyanate (80/20 mixture)

20 grams of "Chlorowax No. 40"

0.5 cc of lead octoate (24% lead)

This blend was cast into a Mylar tray and was found to solidify and beremoved from the Mylar tray as a dense rigid sheet in less than 60seconds after catalyst addition. Appropriate tensile bars were cut fromthis cast resin and were found to exhibit an ultimate tensile of 15,600psi at 10% elongation.

EXAMPLE 61

Same procedure as in Example 1-A employing the following composition:

30 grams of Voranol CP-260

15 grams of toluenediisocyanate (80/20 mixture)

25 grams of hydrogenated methylene diphenyl isocyanate (Hylene W)

10 grams of "Chlorowax No. 40"

1 cc of lead octoate (24% lead)

This blend was cast and was found to suddenly solidify 20 seconds aftercatalyst addition. The rigid casting was demolded 40 seconds aftercatalyst addition and was found to have a density of 1.10 grams/cc.

EXAMPLE 62

Same procedure as in Example 1-A employing the following composition:

300 grams of the reaction product of glycerine with 3 moles of propyleneoxide per mole of glycerine.

400 grams of a prepolymer prepared from the reaction product of 3 molesof propylene oxide per mole of glycerine and toluene diisocyanate, saidprepolymer containing 31% NCO.

300 grams of trichlorobenzene

1 cc of lead octoate (24% Pb)

This liquid blend was cast between 2 parallel sheets of polyethylene;the liquid mix was found to solidify in less than 1 minute aftercatalyst addition and the cast product was removed from the mold in lessthan 2 minutes after catalyst addition. This casting was found to betransparent and bubble-free.

EXAMPLE 63

Same procedure as in Example 1-A employing the following composition:

60 grams of Voranol RS-350

30 grams of toluene diisocyanate (80/20 mixture)

20 grams of 3-methylsulfolane

1 cc of lead octoate (24% Pb)

This liquid blend solidified in less than 30 seconds and was demoldedabout 30 seconds later to yield a hard, transparent, rigid casting.

EXAMPLE 64 A. Example of the Present Invention.

Same procedure as in Example 1-A employing the following composition:

45 grams of Voranol CP-260 (OH equivalent wt. = approx. 87)

45 grams of Hylene TM

30 grams of Voranol CP-4701

0.4 cc of lead octoate (24% Pb)

This blend was cast into a Mylar tray and was found to solidify into atransparent sheet in less than a minute after catalyst addition. Thissheet was removed from the mold in less than 2 minutes after catalystaddition and had physical properties as indicated in the table below.

B. Comparative

Same procedure as in Example 1-A employing the following composition:

105 grams of Voranol CP-700 (OH equivalent wt. = approx. 232)

30 grams of Hylene TM

40 grams of Voranol CP-4701

1 cc of lead octoate (24% Pb)

This blend was also cast into a Mylar tray and was found to solidify 35seconds after catalyst addition. The weak, rubbery transparent castsheet was removed from the mold about 20 seconds after catalyst additionand had properties as indicated in the table below, which shows thatpolyols employed as component A having an OH equivalent weight above 230do not produce the products of the present invention i.e. the %elongation was greater than 80%.

               Ultimate                                                           Polymer    Tensile      Elongation                                                                              Hardness                                    ______________________________________                                        A   (present                                                                      invention) 6540 psi     20%     85 Shore D                                B   (comparative)                                                                             104 psi     92%     45 Shore A                                ______________________________________                                    

The following examples demonstrates the use of byproduct streamscontaining mixtures of aromatic-containing compounds.

EXAMPLE 65

Same procedures as in Example 1-A employing the following composition:

30 grams of the reaction product of glycerine with propylene oxide in amolar ratio of 1:3 respectively, said product having a molecular weightof about 260.

30 grams of a mixed stream of aromatic-containing compounds as theresidue stream obtained from the manufacture of ethyl benzene and havinga typical composition by weight as follows:

3% triethylbenzene

11% tetraethylbenzene

1% pentaethylbenzene

3% bis-ethylphenylethane

8% ethylphenyl-phenylethane

13% 1,1-diphenylethane

61% higher boiling components

30 grams of toluenediisocyanate (80/20 mixture of 2,4- and 2,6-isomers)

1 cc of stannous octoate T-9 (M & T Chemicals)

The blend was cast into a polyethylene mold and suddenly solidifiedwithin 20 seconds after catalyst addition. The rigid, dense casting wasdemolded within 60 seconds after catalyst addition.

EXAMPLE 66 A. Present Invention

Same procedure as in Example 1-A employing the following composition:

60 grams of Voranol RS-350

30 grams of toluene diisocyanate

60 grams of Voranol CP-3000

0.5 cc of lead octoate (24% Pb)

The mixture was cast as a sheet in a Mylar tray and allowed to cureovernight at room temperature.

B. Prior Art Comparison

Same procedure as in Example 1-A employing the following composition:

60 grams of Voranol RS-350

30 grams of toluenediisocyanate

60 grams of dioctylphthalate

0.5 cc of lead octoate (24% Pb)

The mixture was cast as a sheet in a Mylar tray and allowed to cureovernight at room temperature.

C. After curing overnight, each of the panels from A and B above weresprayed with Krylon black enamel in 2 inch wide stripes. After 2 hoursof drying at room temperature, the paint coating was found to be poorlyattached to panel B, an example of the prior art, but was well attachedto panel A, an example of the present invention.

Another portion of each of panels A and B were sprayed with 2 inch widestripes of Illinois Bronze-Powder and Paint Co.' s Flat Black No. 607.The paint dried within an hour on Panel A, the present invention,whereas on Panel B, the prior art, the panel was still tacky after 6hours.

After 72 hours of drying at room temperature, a fingernail scratchremoved paint from panel B, the prior art panel; whereas panel A, thepresent invention, resisted removal of paint by fingernail scratching. Afinger pressure dry rag wipe also removed paint from panel B, the priorart; whereas no paint was removed by this test from panel A, the presentinvention.

Some amine type catalysts will catalyze the urethane reaction to produceinstant set products, but the resultant products are or low density,i.e. less than about 1 gram/cc and contain many bubbles which adverselyaffect the physical properties. This inoperability of the amine typecatalysts insofar as the present invention is concerned is demonstratedby the following comparative Example 67.

EXAMPLE 67 (COMPARATIVE)

A. Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of Voranol CP-3000

30 grams of Hylene TM

1 cc of a 33% solution of diethylenetriamine in dipropyleneglycol.

The mixture slowly set within about 90 seconds to produce an opaque,tacky, rubbery polymer containing many bubbles and having a density of0.6 grams/cc. The casting could be demolded with difficulty within about120 seconds.

B. Same procedure as in Example 1A employing the following composition:

30 grams of Voranol CP-260

30 grams of Voranol CP-3000

30 grams of Hylene TM

2 cc of triethylamine

The mixture slowly set within about 60 seconds which could be demoldedwith difficulty within about 90 seconds. The product was an opaque,rigid solid which had many bubbles and a density of about 0.63 grams/cc.

C. Same procedure as in Example 1A employing the following composition.

30 grams of Voranol CP-260

30 grams of Voranol CP-3000

30 grams of Hylene TM

2 cc of N,N,N',N'-tetramethyl-1,3-butane diamine.

The mixture slowly set within about 120 seconds to produce an opaque,tacky, foam-like product which had a density of 0.51 gram/cc.

The following example demonstrates the superior solvent resistant of thepresent invention as compared to the products of U.S. Pat. No.3,378,511.

EXAMPLE 68 (COMPARATIVE)

Three rigid castings were prepared by the procedure of Example 1-Aemploying the following formulations.

Formulation A (present Invention)

30 grams of the reaction product of glycerine with propylene oxide in amolar ratio of about 1:3 respectively

30 grams of toluene diisocyanate

30 grams of Voranol P-4000

1 cc of lead octoate (24% Pb)

Formulation B (Present Invention)

30 grams of the reaction product of glycerine and propylene oxide at amolar ratio of about 1:3 respectively

30 grams of toluene diisocyanate

20 grams of trichlorobenzene

0.2 cc of lead octoate

Formulation C (Prior Art Teachings -- U.S. Pat. No. 3,378,511)

30 grams of the reaction product of glycerine and propylene oxide in amolar ratio of about 1:3 respectively

30 grams of toluene diisocyanate

30 grams of diisodecyl phthalate

1 cc of lead octoate (24% Pb)

Each of the above formulations A, B and C suddenly solidified into adense, rigid casting within about 30 seconds after catalyst addition andwere demolded within about 60 seconds.

Several 1/4 × 3/4 × 13/4 inches specimens were cut from the castings ofFormulations A, B, and C and immersed in various solvents at roomtemperature. Periodic observations were taken to ascertain the conditionof each specimen after exposure to the solvents. The solvents andobservations are given in the following Table.

                                      OBSERVATION                                 __________________________________________________________________________    SOLVENT    Formulation A                                                                          Formulation B                                                                        Formulation C                                      __________________________________________________________________________    Acetone    no change after                                                                        no change                                                                            severe cracks                                                 1 hr. exposure                                                                         after 1 hr.                                                                          developed after                                                        exposure                                                                             1 hr. exposure                                     Tetrahydrofuran                                                                          slight trace                                                                           not tested                                                                           severe cracking                                               of cracking     and swelling                                                                  after 1 hr.                                                                   exposure                                           Methylene chloride                                                                       slight trace                                                                           no change                                                                            severe cracking                                               of cracking                                                                            after 1 hr.                                                                          with particles                                                after 1 hr.                                                                            exposure                                                                             separating                                                    exposure        from specimen                                                                 after 1 hr.                                                                   exposure.                                          Ethylene dichloride                                                                      intact after                                                                           no change                                                                            developed severe                                              36 hours of                                                                            after 5 hrs.                                                                         cracks after                                                  exposure of exposure                                                                          5 hrs. of exp.,                                                               total disinte-                                                                gration into                                                                  discrete parti-                                                               cles after                                                                    36 hrs. exp.                                       Ethyl Acetate                                                                            no change                                                                              no change                                                                            slight decrepi-                                               after 36 hrs.                                                                          after 7 hrs.                                                                         tation into                                                   of exposure                                                                            of exposure                                                                          discrete parti-                                                               cles after 7                                                                  hrs. and total                                                                disintegration                                                                after 36 hrs.                                                                 exposure.                                          Methylisobutyl                                                                           no change after slight swelling                                    ketone     36 hrs. of                                                                             not    after 36 hrs.                                                 exposure tested of exposure.                                       __________________________________________________________________________

The preceding example clearly demonstrates the superior solventresistance of the composition of the present invention, formulation Aand B, as compared to the prior art, U.S. Pat. No. 3,378,511,formulation C.

EXAMPLE 69

An elastomeric silicone composition was poured around a nominal21/2inches threaded malleable iron pipe plug and cured thereby producingan elastomeric mold of the pipe fitting.

Employing the procedure of Example 1-A, the following composition waspoured into the above prepared mold.

45 grams of Voranol CP-260

68 grams of PAPI

50 grams of Propylene carbonate

1 cc of stannous octoate

The composition suddenly solidified within about 30 seconds aftercatalyst addition and after about another 60 seconds, a polyurethanethreaded pipe plug was removed from the mold. The cast object, pipeplug, had a density greater than 1 gram/cc.

EXAMPLE 70

A 31/2 inches diameter spur gear was removed from a gear box having agear and pinion arrangement and an elastomeric silicone mold of saidspur gear was prepared.

Employing the procedure of Example 1-A, the following composition waspoured into the mold.

60 grams of Voranol CP-260

60 grams of toluene diisocyanate

30 grams of tetrahydronaphthalene

0.2 cc of lead naphthenate (24% Pb)

Within about 25 seconds after catalyst addition, the compositionsuddenly solidified and a rigid polyurethane spur gear was removed fromthe mold after the lapse of an additional 45 seconds. The gear had adensity of greater than 1 gram/cc.

EXAMPLE 71 Preparation of Decorative Article

A sheet of polyethylene was vacuum formed over a half relief sculpturedhorse's head to yield a thin walled polyethylene mold of said horse'shead.

The following non-flexible urethane composition prepared by theprocedure of Example 1-A was poured into the mold:

45 grams of Voranol CP-260

72 grams of an isocyanate terminated prepolymer prepared from toluenediisocyanate and tetrabromobisphenol A, said prepolymer having an NCOcontent of 29.4%.

30 grams of triethylbenzene

1 cc of lead octoate catalyst.

The composition suddenly solidified in about 20 seconds after catalystaddition and within about 60 seconds after catalyst addition a rigidpolyurethane replica of the horse head having a density greater than 1gram/cc was removed from the mold.

EXAMPLE 72

In each of the following experiments, all of the components except thecatalyst were blended together and then the catalyst was added andblended. The resultant mixture was then poured into a 250 ccpolyethylene beaker.

The compositions and results are given in the following table. The timeswere measured from the instant the catalyst was added.

    __________________________________________________________________________                    EXPERIMENT A                                                                          EXPERIMENT B                                                                          EXPERIMENT C                                                  (Present                                                                              (Comparative)                                                                         (Comparative)                                                 Invention)                                                    __________________________________________________________________________    POLYOL.sup.1, grams                                                                           33      33      33                                            TDI.sup.2, grams                                                                              33      33      33                                            ATB.sup.3, grams                                                                              20      20      20                                            NMM.sup.4, cc   0       0.5     0                                             TEDA.sup.5, cc  0       0       0.5                                           PBO.sup.6, cc   0.5     0       0                                             Time for solidification, sec.                                                                 10      >300**  >720***                                       Time solid casting was                                                        removed from the mold, sec.                                                                   20      N.D.*   N.D.*                                         __________________________________________________________________________     *N.D. = not determined.                                                       **Composition was still liquid after 300 seconds.                             ***Composition was still liquid after 720 seconds.                            .sup.1 The polyol employed was the reaction product of glycerine with         propylene oxide to an equivalent weight of about 87.                          .sup.2 TDI = an 80/20 mixture of 2,4-/2,6-toluene diisocyanate having an      NCO equivalent weight of about 87.                                            .sup.3 ATB = acetylene tetrabromide.                                          .sup.4 NMM = N-methylmorpholine.                                              .sup.5 TEDA -- a 33% solution of triethylenediamine in dipropyleneglycol.     .sup.6 PBO = lead octoate containing 24% Pb.                             

EXAMPLE 73

In each of the following experiments, all of the components except thecatalyst were blended together and then the catalyst was added andblended. The resultant mixture was then poured into a 250 ccpolyethylene beaker.

In each of the following experiments, the polyol employed was thereaction product of glycerine with propylene oxide to an equivalentweight of about 87.

In each of the following experiments, the polyisocyanate employed was an80/20 mixture of 2,4-/2,6-toluene diisocyanate (TDI) having an NCOequivalent weight of about 87.

In each of the following experiments acetylene tetrabromide (ATB) wasemployed as the modifier.

In each of the following experiments, the catalysts employed and theirdesignations are as follows:

Dbtdl = dibutyl tin dilaurate

CdOc = cadmium octoate

CoOc = 1 part cobalt octoate dissolved in 2 parts triethyl benzene

Zn = zinc naphthenate

SbOc = antimony octoate

Pmp = 1 part phenyl mercuric propionate in 1 part of propylenecarbonate.

The compositions and results of the experiments are given in thefollowing table.

                     EXPERIMENT NO.                                                                1    2    3    4     5    6                                  __________________________________________________________________________    Polyol, grams    33   33   33   33    33   33                                 TDI, grams       33   33   33   33    33   33                                 ATB, grams       20   20   20   20    20   20                                 DBTDL, cc        0.5  --   --   --    --   --                                 CdOc, cc         --   0.5  --   --    --   --                                 CoOc, cc         --   --   0.5  --    --   --                                 ZN, cc           --   --   --   0.5   --   --                                 SbOc, cc         --   --   --   --    0.5  --                                 PMP, cc          --   --   --   --    --   0.5                                Time* for solidification, sec.                                                                 20   30   20   45    40   30                                 Time* solid casting was                                                       removed from the mold, sec.                                                                    40   60   60   120   90   60                                 Density, g/cc    1.3  1.3  1.3  1.3   1.3  1.3                                __________________________________________________________________________     *The times were measured from the instant the catalyst was added.        

EXAMPLE 74

The procedure of Example 1-A was employed, except that the mixture waspoured into a Mylar tray, with the following components:

40 grams of an adduct of glycerine with 1,2-propylene oxide having anaverage molecular weight of about 260,

40 grams of an 80/20 mixture of 2,4-/2,6-toluene diisocyanate having anNCO equivalent weight of about 87,

40 grams of an ester-modified polyoxyalkylene compound

(I) which was the reaction product of

(a) an adduct of glycerine with propylene oxide, end-capped with about5.2 moles of ethylene oxide per OH group,

(b) about 3 moles of maleic anhydride per mole of (a) and

(c) ethylene oxide: said ester-modified polyoxyalkylene compound havingan average OH equivalent weight of about 1650,

1 cc of lead octoate catalyst containing about 24% lead.

The mixture suddenly solidified within about 30 seconds and was demoldedwithin about 60 seconds after catalyst addition. The solid, rigid castsheet had a density of about >1 g/cc and a tensile strength of about3518 psi at an elongation of 51%.

EXAMPLE 75

The procedure of Example 74 was employed with the following components:

30 grams of an adduct of pentaerythritol with 1,2-propylene oxide havingan OH equivalent weight of about 86,

46 grams of a polymethylene polyphenylisocyanate having an averagefunctionality of about 2.65 and an NCO equivalent weight of about 135,

30 grams of an ester-modified polyoxyalkylene compound (II) that is thereaction product of

(a) an adduct of glycerine with 1,2-propylene oxide having an averagemolecular weight of about 4000,

(b) about 3 moles of phthalic anhydride per mole of (a) and

(c) ethylene oxide; the resultant ester-modified polyoxyalkylenecompound having an average OH equivalent weight of about 1665,

1 cc of T-12 catalyst, a dibutyltin dilaurate catalyst commerciallyavailable from M & T Chemicals.

The mixture suddenly solidified within about 30 seconds and was demoldedwithin about 75 seconds after catalyst addition. The solid, rigid castsheet had a density of about >1 g/cc and a Shore D hardness of about>80.

EXAMPLE 76

The procedure of Example 74 was employed with the following components:

50 grams of an adduct of glycerine and 1,2-propylene oxide having anaverage molecular weight of about 260,

75 grams of an isocyanate-containing prepolymer prepared by reacting anexcess of a mixture of 80/20 2,4-/2,6-toluene diisocyanate with anadduct of glycerine with 1,2-propylene oxide having an average molecularweight of about 260, said prepolymer having about 30% NCO groups byweight and an NCO equivalent weight of about 139.

20 grams of ester-modified polyoxyalkylene compound (I) as defined inExample 74.

20 grams of ester-modified polyoxyalkylene compound (II) as defined inExample 75.

1 cc of a lead octoate catalyst containing about 24% lead.

The mixture suddenly solidified within about 30 seconds and was demoldedwithin about 60 seconds after catalyst addition. The solid, rigid castsheet had a density of about >1 g/cc, a Shore D hardness of about >85and a tensile strength of about 6323 psi at an elongation of about 10%.

We claim:
 1. A non-elastomeric, non-cellular solid polymer having adensity of at least about 1 gram/cc, a percent elongation of less than80, resulting from admixture of the components of a compositioncomprising:A. a polyether polyol having from 3 to about 8 hydroxylgroups and a hydroxyl equivalent weight between about 75 and about 230;B. an organic polyisocyanate; C. a liquid modifier compound having aboiling point above about 150°C selected from the group consisting ofnon-hydroxyl-containing ester-modified polyoxyalkylene compounds havingan average molecular weight above about 700 mixtures thereof, and D. annon-amine-containing catalyst for urethane formation, which is anorganometal compound;wherein components (A) and (B) are present inamounts so as to provide an NCO:OH ratio of from about 0.8:1 to about2:1, component (C) is present in quantities of from about 20 to about 50percent with the proviso that when component (B) is a prepolymercontaining less than about 40% NCO groups by weight, then component (C)is present in quantities of from about 10% to about 50% by weight of thesum of components (A), (B) and (C); and component (D) is present inquantities of from about 0.2 to about 10 percent by weight of the sum ofthe weights of components (A), (B) and (C); and wherein said polymer canbe demolded within less than about 5 minutes without the application ofan external source of heat, after admixture of said composition.
 2. Thecomposition of claim 1 wherein components (A) and (B) are present inquantities such that the NCO:OH ratio of the (A) and (B) components isfrom about 0.95:1 to about 1.1:1, component (C) is present in quantitiesof from about 30 to about 50 percent by weight of the sum of components(A), (B) and (C) and wherein component (D) is present in quantities offrom about 0.5 to about 3 percent by weight of the sum of the weights ofcomponents (A), (B), and (C).
 3. The composition of claim 2 whereincomponent (D) is an organo-metal compound of a metal selected from tin,zinc, lead, mercury, cadmium, bismuth and antimony.
 4. The compositionof claim 3 wherein component (D) is an organo-tin compound or anorgano-lead compound.
 5. The composition of claim 4 wherein component(C) is a non-hydroxyl-containing ester-modified glycerine initiatedpolyoxyalkylene compound.
 6. The articles resulting from casting thecompositions of claim
 1. 7. The articles of claim 6 wherein saidarticles are furniture components.
 8. The articles of claim 6 whereinsaid articles are decorative objects.
 9. The articles of claim 6 whereinsaid articles are machine components.
 10. A process for productingsolid, rigid, polyurethane articles having a density of at least 1 g/cc,a percent elongation of less than 80, and which can be demolded within aperiod of about 5 minutes without the addition of an external source ofheat which process comprises:1. admixing the components of a compositioncomprisingA. a polyether polyol having from 3 to about 8 hydroxyl groupsand a hydroxyl equivalent weight between about 75 and about 230, B. anorganic polyisocyanate, C. a liquid modifier compound having a boilingpoint about about 150°C selected from the group consisting ofnon-hydroxyl-containing ester-modified polyoxyalkylene compounds havingan average molecular weight above about 700 and mixtures thereof, and D.a non-amine-containing catalyst for urethane formation, which is anorgano metal compound; wherein components (A) and (B) are present inamounts so as to provide an NCO:OH ratio of from about 0.8:1 to about2:1, component (C) is present in quantities of from about 20 to about 50percent with the proviso that when component (B) is a prepolymercontaining less than about 40% NCO groups by weight, then component (C)is present in quantities of from about 10% to about 50% by weight of thesum of components (A), (B) and (C) and component (D) is present inquantities of from about 0.2 to about 10 percent by weight of the sum ofthe weights of components (A), (B) and (C); and wherein said polymer canbe demolded within less than about 5 minutes, without the application ofan external source of heat, after admixture of said composition; 2.placing the admixed composition into a suitable mold wherein saidcomposition solidifies within less than about 5 minutes to a solidhaving the aforesaid density and elongation; and
 3. subsequentlydemolding the resultant articles from the mold.
 11. The process of claim10 wherein components (A) and (B) are present in quantities such thatthe NCO:OH ratio is the (A) and (B) components is from the about 0.95:1to about 1.1:1, component (C) is present in quantities of from about 30to about 50 percent by weight of the sum of components (A), (B), and (C)and wherein component (D) is present quantities of from about 0.5 toabout 3 percent by weight of the sum of the weights of components (A),(B) and (C).
 12. The process of claim 10 wherein component (D) is anorgano-metal compound of a metal selected from tin, zinc, lead, mercury,cadmium, bismuth and antimony.
 13. The process of claim 12 whereincomponent (D) is an organo-tin compound or an organo-lead compound. 14.The process of claim 13 wherein component (C) is anon-hydroxyl-containing ester-modified glycerine initiatedpolyoxyalkylene compound.
 15. The process of claim 10 wherein said moldis that of a furniture component.
 16. The process of claim 10 whereinsaid mold is that of a decorative object.
 17. The process of claim 10wherein said mold is that of a machine component.